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US20030022795A1 - Thin film Hg-based superconductors, thermoelectric materials and methods of fabrication thereof - Google Patents

Thin film Hg-based superconductors, thermoelectric materials and methods of fabrication thereof Download PDF

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US20030022795A1
US20030022795A1 US10/022,011 US2201102A US2003022795A1 US 20030022795 A1 US20030022795 A1 US 20030022795A1 US 2201102 A US2201102 A US 2201102A US 2003022795 A1 US2003022795 A1 US 2003022795A1
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Judy Wu
Shaolin Yan
Yiyuan Xie
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/01—Manufacture or treatment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen
    • H10N10/8552—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen the compounds being superconducting
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00—Superconducting devices
    • H10N60/01—Manufacture or treatment
    • H10N60/0268—Manufacture or treatment of devices comprising copper oxide
    • H10N60/0296—Processes for depositing or forming copper oxide superconductor layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00—Superconducting devices
    • H10N60/01—Manufacture or treatment
    • H10N60/0268—Manufacture or treatment of devices comprising copper oxide
    • H10N60/0296—Processes for depositing or forming copper oxide superconductor layers
    • H10N60/0548—Processes for depositing or forming copper oxide superconductor layers by deposition and subsequent treatment, e.g. oxidation of pre-deposited material
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00—Superconducting devices
    • H10N60/80—Constructional details
    • H10N60/85—Superconducting active materials
    • H10N60/855—Ceramic superconductors
    • H10N60/857—Ceramic superconductors comprising copper oxide

Definitions

  • the present invention is broadly concerned with improved methods for forming superconducting materials and thermoelectric materials comprising highly volatile elements.
  • the methods are useful for the production of highly epitaxial Hg-containing film superconductors exhibiting very high J c values, along with novel films of this character.
  • the methods are useful for the production of thermoelectric materials which have very low thermal conductivities.
  • a process is carried out whereby precursor structures including a nonvolatile element are subjected to energy in the presence of a vapor comprising a volatile element so as to cause the nonvolatile element to be replaced by the volatile element without substantial alteration of the crystalline structure of the precursor.
  • Hg-based superconductors have a record high superconducting transition temperature (T c ⁇ 135K). Since a higher T c promises higher device operation temperature and a better stability at a given temperature, it is very important to develop viable technologies for fabrication of high-quality Hg-based superconducting films.
  • Prior technologies generally involve two steps: deposition of amorphous rare-earth cuprate precursor films with or without Hg, followed by Hg-vapor annealing at temperatures above 800° C. under a controlled Hg-vapor pressure in order to form the superconducting phases.
  • All high T c superconductors have layered structures and their physical properties are anisotropic parallel or perpendicular to the layers. The alignment of grains during the growth is crucial for the quality of the films. Since most applications of the superconductor require the capability of carrying high current, epitaxial growth of grains is essential.
  • Hg-based compounds are volatile, the control of the growth conditions is very difficult using conventional techniques.
  • c-axis-oriented superconducting Hg-1212 and Hg-1223 films have been obtained with their T c up to 124K and 130K, respectively, high-quality epitaxial growth has not been achieved.
  • the superconducting grains are connected more or less randomly in the plane of the substrates. This lack of epitaxy is reflected in the poor x-ray pole figures and high X min values of prior Hg-1212 and Hg-1223 films, which are on the order of 100%.
  • a direct effect of this substantial non-epitaxy is that the J c values of the films are much lower than expected in view of the intragrain J c values and the high irreversibility line of the Hg-based superconductors. When current passes grain boundaries, it is significantly reduced owing to the fact that the grains are not aligned epitaxially.
  • the other effect of this non-epitaxy is a relatively rough film surface which hinders many potential applications of the Hg-based superconducting thin films, e.g., for use in microelectronics.
  • Hg-based superconductors are so delicate and tend to react with etching chemicals and water
  • fabrication of the Hg-containing micro-bridges directly from Hg-containing films using regular photolithography processes generally results in degradation of the samples. This, in turn, leads to unreliable connections in the circuit.
  • Current state-of-the-art Peltier refrigerators use semiconducting Bi 2 Te 3 -Sb 2 Te 3 alloys (with a ZT of ⁇ 1) that only produce moderate amounts of cooling and are inefficient compared to compressor-based refrigerators. As a result, thermoelectric refrigerators are generally used in applications where reliability and convenience are more important than economy.
  • thermoelectric materials having a higher ZT.
  • a solid that is simultaneously a poor conductor of heat and a good conductor of electricity could have a ZT as high as 2-4, making it ideal for thermoelectric applications.
  • Filled skutterudites have the general formula RM 4 X 12 , where typically: X is P, As, or Sb; M is Fe, Ru, or Os; and R is La, Ce, Pr, Nd, or Eu.
  • Skutterudites are body-centered, cubic crystals with 34 atoms in the conventional unit cell and a space group of Im3. This structure consists of square, planar rings of four pnicogen atoms (i.e., X from the general formula) with rings of four oriented along either the (100), (010), or (001) crystallographic directions.
  • the metal atoms M form a simple cubic sublattice, and the rattler atoms R are positioned in the two remaining holes in the unit cell.
  • the structure of filled skutterudites differs from basic skutterudites in that basic skutterudites do not contain a rattler atom R. It has previously been shown that the ⁇ lattice of filled skutterudite antimonides is nearly an order of magnitude lower than that of the basic skutterudites due to the presence of the rattling atoms R.
  • the present invention overcomes the problems outlined above and provides new methods for the production of desirable high T c and J c (both magnetic and transport) value Hg-containing film superconductors having significantly improved epitaxial characteristics.
  • transport J c refers to the measure of current density through a film when a current is directly applied to the film
  • magnetic J c refers to the measure of current density through a film that is induced by the application of a magnetic field to the film.
  • the present invention also provides methods for the production of thermoelectric materials having high ZT's and low -thermal conductivities.
  • ZT TS 2 / ⁇ , where T is the maximum operating temperature of the material, S is the Seebeck coefficient, ⁇ is the resistivity, and ⁇ is the thermal conductivity of the material.
  • the processes of forming superconductor films involves initial production of T1-based superconducting films using known T1-vapor annealing techniques, followed by Hg-vapor annealing to replace at least a portion of the T1 by Hg so that the desired Hg-based superconducting films are obtained.
  • T1-based superconducting films have similar crystalline structures to Hg-based superconducting films, but the T1 and especially J c values at high temperature above 77K of the T1-films are much lower. However, T1 is much less volatile than Hg and has a higher sticking coefficient.
  • T1-based superconducting films that have greatly superior epitaxial properties (i.e., the grains are more uniformly aligned and are not randomly positioned on the substrate) compared to prior art films.
  • T1 is driven out of the starting films and replaced by Hg simultaneously.
  • time/temperature annealing conditions it has been found that this exchange can occur without significantly altering the overall crystalline structure, so that high quality epitaxial Hg-based superconducting films can be obtained.
  • the methods of the invention broadly involve first providing a body made up of a substrate having a T1-based superconducting film supported on a surface thereof, followed by annealing the body in the presence of Hg vapor and under conditions whereby at least a portion of the T1 of the starting superconducting film is replaced by Hg.
  • this Hg-vapor annealing is carried out at a temperature of from about 600-900° C. for a period of from about 1-20 hours, and more preferably at a temperature of from about 640-800° C. for a period of from about 2-15 hours.
  • the T1-based superconducting film is patterned and etched using conventional photolithography and etching techniques (i.e., a photoresist composition is applied to the film, exposed to activating radiation, developed, and etched).
  • a photoresist composition is applied to the film, exposed to activating radiation, developed, and etched.
  • the remaining T1 film and newly formed micro-bridges are then annealed in the presence of Hg vapor as described above.
  • the width of the micro-bridges is generally from about 2-10 m.
  • T1-based starting superconducting films for making Hg-1212 superconducting films are selected from the group consisting of T1-1212 and T1-2212 films (i.e., T1Ba 2 CaCu 2 O 7 and T1 2 Ba 2 CaCu 2 O 8 ), preferably yielding HgBa 2 CaCu 2 O x films wherein x ranges from about 5.8-6.2.
  • T1-based starting superconducting films for making Hg-2223 superconducting films are selected from the group consisting of T1-1223 and T1-2223 (i.e., T1Ba 2 Ca 2 Cu 3 O 9 and T1 2 Ba 2 Ca 2 Cu 3 O 105 ), preferably yielding HgBa 2 Ca 2 Cu 30 x films wherein x ranges from about 7.8-8.2. These are generally formed on a substrate, usually a single crystal substrate such as LaAlO 3 , by known techniques to form a highly epitaxial film.
  • FIG. 1 sets forth a number of different orientations of the starting T1-film bodies (shown as rectangles) with respect to a superconducting Hg-containing pellet and optionally in the presence of a Ba—Ca—Cu—O oxide pellet. It will be understood that these various annealing configurations are in practice preferably placed within a quartz tube (not shown in FIG. 1) whereupon a vacuum (on the order of from about 10 ⁇ 4 to 1 Torr) is drawn and the tube is sealed. This sealed tube is then placed within the annealing furnace.
  • the final Hg-containing films are preferably either Hg-1212 or Hg-1223 films and usually have a thickness of from about 0.005-500 ⁇ m and more preferably from about 0.1-1 ⁇ m.
  • J c values are quite significant because the prior art Hg-containing films, and particularly Hg-1212 films, have only been able to achieve J c values of 10 6 A/cm 2 at 77K and zero magnetic field. Furthermore, these prior art J c values are magnetic J c values and not transport J c values. Because J c depends on both the superconductivity of the molecule applied to the substrate as well as the manner in which the molecule grains are positioned on the substrate (i.e., the epitaxy), the current densities of films at higher temperatures are unpredictable based upon the current densities of the films at lower temperatures.
  • Hg-containing films of the invention The highly epitaxial character of the Hg-containing films of the invention is confirmed by the x-ray pole figures and X min values thereof which are up to about 50%, and more preferably from about 10-40%.
  • Hg-1212 films according to the invention have a low microwave surface resistance of less than about 0.4 m ⁇ and preferably less than about 0.3 m ⁇ at 120K, values that have never been obtained above 100K in prior art superconductors.
  • thermoelectric materials comprises providing, in a reaction vessel, a three-dimensional, crystalline precursor comprising a plurality of atoms and at least one molecule weakly bonded thereto.
  • molecule is intended to include elements as well as ions derived from those elements.
  • lanthanum molecule is intended to include elemental lanthanum as well as lanthanum ions.
  • the precursor is then perturbed, causing the bond(s) between the molecule and the atoms to break, thus releasing the molecule from the precursor.
  • the perturbing step can be accomplished by any method which subjects the crystalline precursor to energy of perturbation. Suitable methods include heat, light, ion beams, etc. When heat is utilized, the temperature to which the precursor is heated should be at least about 500° C., and preferably at least about 1000° C., depending upon the particular molecule which is weakly bonded to the precursor.
  • vapor under a controlled pressure and comprising a second molecule is introduced into the reaction vessel so that the second molecule replaces the released first molecule within the precursor.
  • the remaining crystalline structure of the precursor i.e., structure other than the first molecule
  • the remaining crystalline structure of the precursor remains essentially unaltered during this process.
  • any crystalline structure can be utilized as the crystalline precursor in the inventive processes, with body-centered crystals, orthorhombic crystals (such as perovskites), and cubic crystals being particularly preferred.
  • body-centered crystal is the skutterudite having the general formula RM 4 X 12 , where M is a metal atom and R is a “rattler.”
  • Preferred metal atoms M are Fe, Ru, and Os, while preferred rattlers R (for use as the first molecule) are selected from the group consisting of La, Ce, Pr, Nd, and Eu.
  • “X” in the general formula RM 4 X 12 is preferably a pnicogen atom (e.g., P, As, Sb).
  • any volatile molecule that is desired in the precursor at the same location as the first molecule can be utilized as the second molecule.
  • the same definition of molecule discussed above is intended to apply with respect to the second molecule.
  • suitable candidates for second molecules include those selected from the group consisting of Pb, Hg, Sn, In, T1, and Ga. Because the second molecule is more volatile than the first molecule, it will have increased “rattling” abilities compared to the first molecule (i.e., increased local anharmonic vibrations around the rattler site).
  • thermoelectric materials have a phonon thermal conductivity ( ⁇ lattice ) at room temperature of less than about 0.012 W/cm-K, preferably less than about 0.01 W/cm-K, and more preferably less than about 0.007 W/cm-K.
  • This low - ⁇ lattice contributes to thermoelectric materials having a ZT of at least about 2, preferably at least about 3, and more preferably at least about 3.5.
  • FIG. 1 is a schematic representation of a number of exemplary annealing configurations which can be used in the preparation of the thin film superconductors of the invention
  • FIG. 2 is a scanning electron micrograph (SEM) of an exemplary Hg-1212 film (Run No. 3 of the Example) exhibiting condensed plate-like grains;
  • FIG. 3 is a series of XRD ⁇ -2 ⁇ scans of a T1-2212 original film and two Hg-1212 films (TLHG-C and SY1112L refer to Runs Nos. 3 and 14, respectively) after substitution conversion from T1-2212 films;
  • FIG. 4 is a series of XRD ⁇ -2 ⁇ scans of a T1-1212 original film and two Hg-1212 films (X971202 and X971123 refer to Runs Nos. 20 and 24, respectively) after substitution conversion from T1-1212 films;
  • FIG. 5 is a series of critical transition curves of an original T1-2212 film and of some Hg-1212 films after substitution conversion from T1-2212 films (TLHG.D, SY1112, TLHG.F, TLHG.G, TLHG.H, TLHG.L2, TLHG.C, TLHG.I and TLHG.J refer to Runs Nos. 4, 14, 5, 10, 11, 9, 3, 6 and 7, respectively);
  • FIG. 6 is a series of critical transition curves of an original T1-1212 film and some Hg-1212 films after substitution conversion from T1-1212 films (TH1212B, Y980121, X971204, TH1212A, X971126, X971123 and X971202 refer to Runs Nos. 23, 22, 25, 21, 26, 24 and 20, respectively);
  • FIG. 7 is an XRD pole figure of a Hg-1212 film (Run No. 3);
  • FIG. 8 is a series of critical current densities of an original T1-2212 film and of three Hg-1212 films after substitution conversion from T1-2212 films (SY1112L, TLHG.C, TLHG.D refer to Runs Nos. 14, 3 and 4, respectively);
  • FIG. 9 is a series of critical current densities of an original T1-1212 film and of five Hg-1212 films after substitution conversion from T1-1212 films (TH1212A, TH1212B, X971123, X971126, X971202 and X971204 refer to Runs Nos. 21, 23, 24, 26, 20 and 25, respectively);
  • FIG. 10 is a graphical comparison of the critical current density (J c ) of representative Hg-1212 film (Run No. 3) and T1-2212 film in different magnetic fields at 60 K, 77 K and 100 K;
  • FIG. 11 is a graph illustrating the critical current density of a representative Hg-1212 film (Run No. 3) at varying magnetic fields and at different temperatures;
  • FIG. 12 is a graph similar to that of FIG. 11 and illustrates a series of critical current density readings for the same Hg-1212 film (Run No. 3) in lower magnetic fields ( ⁇ 0.1 T) and at higher temperatures ( ⁇ 70 K);
  • FIG. 13 is a graph illustrating RBS/channeling results with a representative Hg-1212 film (Run No. 4); the calculated X min ⁇ 40% indicates the alignment of more than 60% of the grains of the film in the plane of the LaAlO 3 (001) substrate;
  • FIG. 14 is a graph illustrating the transport critical current density (J c ) at varying temperatures of an Hg-1212 film prepared according to the processes of the invention.
  • FIG. 15 is a graph illustrating the microwave surface resistance of T1-2212 and Hg-1212 films processed according to the processes of the invention.
  • FIG. 16 is an SEM photograph showing Hg-vapor annealed T1-2212 micro-bridges having widths of 20 ⁇ m, 10 ⁇ m, and 2 ⁇ m at magnifications of 2000 ⁇ , 1500 ⁇ , and 3000 ⁇ ;
  • FIG. 17 is an SEM photograph (1100 ⁇ ) showing Hg-1212 micro-bridges having widths of 20 ⁇ m and 10 ⁇ m;
  • FIG. 18 is a graph illustrating the resistance vs. temperature behaviors of H-1212 micro-bridges processed according to the processes of the invention and annealed at 780° C.;
  • FIG. 19 is a graph illustrating the resistance vs. temperature behaviors of H-1212 micro-bridges processed according to the processes of the invention and annealed at 700° C.;
  • FIG. 20 is a graph illustrating the transport critical density (J c ) at varying temperatures of Hg-1212 micro-bridges having varying widths and processed according to the processes of the invention and annealed at 780° C. (“HT”) and 700° C. (“LT”).
  • J c transport critical density
  • Examples 1-4 are directed towards methods of forming superconducting films according to the processes of the invention.
  • a series of Hg-1212 epitaxial films were produced using the Hg substitution technique.
  • a series of approximately 3 ⁇ 3 ⁇ 0.5 mm single crystal lanthium aluminate (LaAlO 3 ) blocks were provided.
  • a surface of each of these blocks was coated with either T1-2212 (T1 2 Ba 2 CaCu 2 O 8 ) or T1-1212 (T1Ba 2 CaCu 2 O 8 ) using the DC magnetron sputtering technique as described by Yan et al., Appl. Phys. Lett., 63:1845 (1993); Yan et al, Supercond. Sci. Technol., 7:681 (1994) and Siegal et al, J. Mater.
  • the coated blocks were annealed at a temperature of about 740-780° C. for a period of about 6 hours in an enclosed crucible formed of either solid T1 2 Ba 2 CaCu 2 O 8 (for the T1-2212 coated blocks) or T1Ba 2 CaCu 2 O 65 (for the T1-1212 coated blocks), with pure argon gas.
  • These epitaxial films had a thickness of about 0.3 ⁇ m. The epitaxial nature of the films was confirmed by XRD pole figure and RBS/channeling.
  • each of the blocks was subjected to Hg substitution to create epitaxial Hg-1212 films thereon.
  • Hg-containing body Hg 1-y Ba 2 Ca 2 Cu 3 O x , wherein y ranged from 0-0.5
  • an additional body of non Hg-containing oxide a mixture of BaO, CaO and CuO in a nominal 223 ratio
  • quartz tube 7. mm I.D., 10 mm O.D., 2.5 cm in length.
  • One end of the quartz tube was then closed and a vacuum ( ⁇ 10 ⁇ 2 Torr) was drawn in the tube, whereupon the remaining end of the quartz tube was fused.
  • the closed quartz tube was then placed within an elongated stainless steel pipe (about 1 ⁇ 2 inch I.D.) and this was placed within a conventional tube furnace. At this point, the contents of the quartz tube were heated at an ascending rate of 10-50° C./min. to an annealing temperature, the annealing temperature was held for a period of hours (annealing period), and thereafter the quartz tube was furnace cooled until ambient temperature was reached.
  • the Hg-containing bodies were in the form of cylindrical pellets (6 mm diameter ⁇ 4-10 mm length) and in some cases these were slotted to receive the previously coated blocks. In other instances, the blocks were placed adjacent one end of the Hg-containing superconducting body, or sandwiched between two such bodies. Similarly, where the precursor bodies were used, these were in the form of 6 mm diameter pellets of variable length.
  • FIG. 1 illustrates various exemplary block/pellet configurations, some of which were used in these experiments.
  • the Hg-containing and non-Hg-containing bodies can be reacted or unreacted.
  • the individual blocks having the substitution-formed Hg-1212 epitaxial superconducting thin films thereon were recovered and further annealed in a tube furnace at a temperature of 300-350° C. for a period of from about 1-10 hours in a flowing oxygen enviromnent to maximize the T c of the final films.
  • the furnace was heated at a rate of approximately 15° C./min. up to 300° C., and after the annealing was completed, the blocks were cooled by turning off the furnace power.
  • Table 1 below sets forth the annealing conditions employed in the formation of the Hg-1212 superconducting films using the T1-2212-coated blocks.
  • TABLE 1 Pellet Composition Annealing Annealing Temperature Period Annealing Configuration Wt. Ratio of Hg-Pellet to Run # (° C.) (Hrs.) (see Fig.
  • Table 2 sets forth the characterizing data developed from testing the films of Table 1.
  • TABLE 2 Run T c J c ( ⁇ 10 6 A/cm 2 ) Phase Purity # (K) 5K 77K 100K (%)
  • Surface Morphology Structure 1 115 1.63 — — 93.6 Plate-like grains and impurity C-axis particles oriented 2 115 5.79 0.38 0.13 94.2 Plate-like grains and impurity C-axis particles oriented 3 120 13.1 2.23 0.91 89.6 Bright, dense plate-like grains C-axis oriented 4 120 14.0 2.78 0.95 79.9 Bright, plate-like grains and small C-axis holes oriented 5 120 10.9 1.12 0.37 85.4 Bright, dense plate-like grains C-axis and small holes oriented 6 120 14.9 1.57 0.53 66.5 Plate-like grains and small holes C-axis oriented 7 117 10.5 0.94 0.26 76.5 Plate-like grains and small holes C-axis oriented 8 122 6.1 0.70 0.20 88.8 Plate-
  • Table 3 gives the annealing conditions used in the formation of the Hg-1212 superconducting films using the T1-1212-coated blocks. TABLE 3 Annealing Annealing Film and Run Temperature Period Pellets Pellet Composition Wt.
  • Table 4 gives the characterizing data developed from testing the films of Table 3.
  • FIGS. 2 - 13 further exemplify the characteristics of the Hg-containing superconducting thin films of this example.
  • critical temperature transition curves are provided which confirm that the T c values of the T1-containing films are substantially lower than those of the substituted Hg-containing films.
  • FIGS. 8 - 10 set forth critical current density data and establishes that at high temperature (>90K), the critical current densities of the Hg-1212 films are much larger than those of the T1-1212 and T1-2212 films.
  • an Hg-1212 epitaxial film was produced following the procedures set forth in Example 1.
  • the resultant Hg-substituted thin film superconductor was evaluated for transport J c at 100K and varying magnetic fields. The results of this evaluation are depicted in FIG. 14 where it can be seen that the transport J c at zero magnetic field was 10 6 A/cm 2 .
  • an Hg-1212 epitaxial film was prepared following the procedures set forth in Example 1.
  • the intermediate T1-2212 film and the resultant Hg-substituted film were evaluated for their microwave surface resistance at 10 GHz and varying temperatures. As illustrated in FIG. 15, at 115 K and 10 GHz, a resistance of 0.3 milliohms was observed for the Hg-1212 films. This resistance has never been achieved at 115K by prior art films.
  • T1-2212 films were prepared as described in Example 1.
  • the films were then etched using conventional photolithography processes to form micro-bridges of various widths in the film.
  • the T1 forming the micro-bridges was then replaced by Hg also as described in Example 1, with three micro-bridges each being annealed at 780° C. for 3 hours (SEM of bridges shown in FIG. 16) and two micro-bridges each being annealed at 700° C. for 12 hours 10 (SEM of bridges shown in FIG. 17).
  • FIGS. 18 and 19 depict the resistivity versus temperature of the bridges while FIG. 20 illustrates the transport J c .
  • T c values of these micro bridges are in the range of 110-120K and the transport Jc values are in the range of 0.5 to 2.3 ⁇ 10 6 A/cm 2 at 100K and 0 magnetic field.
  • a value of 2.3 ⁇ 10 6 A/cm 2 at 100K has not been achieved by prior art superconductors.
  • a precursor matrix is selected.
  • the matrix should have a similar structure and composition to that of the final, target material.
  • the matrix should also have at least one weakly bonded molecule (e.g., “molecule A”) which will be replaced by the desired molecule (e.g., “molecule B”) to form the target material.
  • Molecule A is perturbed (i.e., energy is applied to the precursor matrix), causing molecule A to vibrate around the equilibrium site where the Gibbs free 25 energy is minimized. It will be appreciated that the spacial deflection of molecule A is proportional to the energy of perturbation.
  • the perturbation energy is maintained close to, but below, the threshold perturbation energy (U th ).
  • U th is the point at which the deflection of molecule A would be comparable to the lattice constant, thus causing the precursor matrix to collapse as a result of the rapid escape of many molecules A from the matrix.
  • U th the threshold perturbation energy
  • the overall structure of the precursor is maintained while allowing molecule A to slowly escape.
  • a vapor of molecule B is simultaneously introduced, resulting in a molecule B replacing essentially each molecule A as it escapes from the structure.
  • Skutterudites filled with volatile rattlers can be fabricated from basic skutterudites (i.e., MX 3 , where M is a metal atom and X is preferably a pnicogen atom) or from skutterudites filled with less volatile (relative to the rattlers) molecules.
  • MX 3 basic skutterudites
  • X is preferably a pnicogen atom
  • This process offers numerous advantages over the prior art. First, it is a kinetic process that can be carried out over a wide processing window in contrast to the narrow processing window required by the phase equilibrium of conventional thermal reaction processes. Also, the exchange occurs at an atomic scale. Therefore, the generated compound inherits the qualities (e.g., phase purity, crystalline structure, surface morphology) of the precursor matrix. This makes synthesis of the compounds much simpler and improves the quality of the final compounds as the precursor matrices are generally readily obtainable in high quality forms.
  • qualities e.g., phase purity, crystalline structure, surface morphology
  • Basic, non-filled skutterudites are prepared according to the known prior art methods.
  • the skutterudites are then heated in an evacuated vessel to temperatures of from about 500-1000° C.
  • Hg vapor is simultaneously introduced into the vessel at a vapor pressure of from about 1-10 atm, causing Hg molecules to fill the skutterudites after a time period of about 30-200 minutes.
  • Skutterudites filled with Pb molecules are prepared according to known prior art methods.
  • the Pb-filled skutterudites are then heated in an evacuated vessel to a temperature of at least about 500° C. While the vessel is maintained at this temperature, Hg vapor is introduced into the vessel at a vapor pressure of from about 1-10 atm so that Hg molecules replace the Pb molecules as they are released from the skutterudites, forming skutterudites filled with Hg molecules.

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  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

Improved Hg-containing superconducting films and thermoelectric materials are provided. The films are fabricated by annealing starting T1-containing films (e.g., T1-1212 or T1-2212) in an Hg-vapor environment so as to cause a substitution of T1 by Hg without substantial alteration of the crystalline structure of the starting films. Preferably, a body comprising a substrate having an epitaxial T1-containing film thereon is annealed under vacuum conditions with a Hg-based bulk; typical annealing conditions are 600-900° C. for a period of from about 1-20 hours. The final Hg-containing film products have a Jc of at least about 106 A/cm2 (100 K, OT) and a Xmin of up to about 50%. The thermoelectric materials are prepared by perturbing a crystalline precursor having a structure similar to the final material so as to cause a first molecule to be released from the precursor. A vapor is introduced into the reaction system simultaneous to or shortly after the perturbation step so as to cause molecules which are within the vapor and are different than the first molecules to replace the first molecules in the precursor.

Description

    RELATED APPLICATIONS
  • This application is a divisional of application Ser. No. 09/843,965, filed Apr. 27, 2001, which is a divisional of application Ser. No. 09/427,428, filed Oct. 26, 1999, which is a continuation-in-part of U.S. patent application Ser. No. 09/299,200, filed Apr. 23, 1999, which is a continuation-in-part of U.S. patent application Ser. No. 09/067,401, filed Apr. 27, 1998, now abandoned.[0001]
    • BACKGROUND OF THE INVENTION
  • 1. Field of the Invention [0002]
  • The present invention is broadly concerned with improved methods for forming superconducting materials and thermoelectric materials comprising highly volatile elements. In one embodiment, the methods are useful for the production of highly epitaxial Hg-containing film superconductors exhibiting very high J[0003] c values, along with novel films of this character. In another embodiment, the methods are useful for the production of thermoelectric materials which have very low thermal conductivities. In either embodiment, a process is carried out whereby precursor structures including a nonvolatile element are subjected to energy in the presence of a vapor comprising a volatile element so as to cause the nonvolatile element to be replaced by the volatile element without substantial alteration of the crystalline structure of the precursor.
  • 2. Description of the Prior Art [0004]
  • Hg-based superconductors have a record high superconducting transition temperature (T[0005] c˜135K). Since a higher Tc promises higher device operation temperature and a better stability at a given temperature, it is very important to develop viable technologies for fabrication of high-quality Hg-based superconducting films. Prior technologies generally involve two steps: deposition of amorphous rare-earth cuprate precursor films with or without Hg, followed by Hg-vapor annealing at temperatures above 800° C. under a controlled Hg-vapor pressure in order to form the superconducting phases.
  • All high T[0006] c superconductors have layered structures and their physical properties are anisotropic parallel or perpendicular to the layers. The alignment of grains during the growth is crucial for the quality of the films. Since most applications of the superconductor require the capability of carrying high current, epitaxial growth of grains is essential.
  • Since Hg-based compounds are volatile, the control of the growth conditions is very difficult using conventional techniques. Though c-axis-oriented superconducting Hg-1212 and Hg-1223 films have been obtained with their T[0007] c up to 124K and 130K, respectively, high-quality epitaxial growth has not been achieved. In other words, the superconducting grains are connected more or less randomly in the plane of the substrates. This lack of epitaxy is reflected in the poor x-ray pole figures and high Xmin values of prior Hg-1212 and Hg-1223 films, which are on the order of 100%.
  • A direct effect of this substantial non-epitaxy is that the J[0008] c values of the films are much lower than expected in view of the intragrain Jc values and the high irreversibility line of the Hg-based superconductors. When current passes grain boundaries, it is significantly reduced owing to the fact that the grains are not aligned epitaxially. The other effect of this non-epitaxy is a relatively rough film surface which hinders many potential applications of the Hg-based superconducting thin films, e.g., for use in microelectronics.
  • The volatility of Hg presents a particular problem in the fabrication of micro-bridges in microelectronic devices. Because Hg-based superconductors are so delicate and tend to react with etching chemicals and water, fabrication of the Hg-containing micro-bridges directly from Hg-containing films using regular photolithography processes generally results in degradation of the samples. This, in turn, leads to unreliable connections in the circuit. [0009]
  • There is accordingly a real and unsatisfied need in the art for an improved method of fabricating Hg-containing superconductors to yield films having a high degree of epitaxy and correspondingly high T[0010] c and Jc values.
  • The properties of thermoelectric materials are demonstrated by calculating the figure of merit ZT=TS[0011] 2/κρ, where T is the operating temperature of the material, S is the Seebeck coefficient, ρ is the resistivity, and κ is the thermal conductivity of the material. Current state-of-the-art Peltier refrigerators use semiconducting Bi2Te3-Sb2Te3 alloys (with a ZT of <1) that only produce moderate amounts of cooling and are inefficient compared to compressor-based refrigerators. As a result, thermoelectric refrigerators are generally used in applications where reliability and convenience are more important than economy.
  • Many attempts have been made to design improved thermoelectric materials having a higher ZT. Theoretically, a solid that is simultaneously a poor conductor of heat and a good conductor of electricity (the “electron crystal and phonon glass”) could have a ZT as high as 2-4, making it ideal for thermoelectric applications. [0012]
  • It has been proposed that synthesizing semiconducting compounds in which one of the atoms or molecules is weakly bound in an oversized atomic cage would cause the weakly bound atom to undergo local anharmonic vibrations, somewhat independent of the other atoms in the crystal, forming what is known as a “rattler.” These localized rattlers can, in some cases, dramatically lower the phonon thermal conductivity (κ[0013] lattice) to values comparable to that of a glass of the same composition. The theoretical lower limit of κlattice is designated κmin and corresponds to the thermal conductivity of an amorphous solid in which the mean-free path of the heat-carrying phonons approaches the order of the phonon wavelength. In an electrically conducting solid, heat is transported by both the charge carriers (electrons or holes) and phonons (lattice); hence, κ=κelectron+κlattice. Therefore, a significantly enhanced ZT is expected from a minimized κlattice.
  • One class of materials that satisfies many of the requirements of an electron-crystal and phonon-glass solid is the filled skutterudites. Filled skutterudites have the general formula RM[0014] 4X12, where typically: X is P, As, or Sb; M is Fe, Ru, or Os; and R is La, Ce, Pr, Nd, or Eu. Skutterudites are body-centered, cubic crystals with 34 atoms in the conventional unit cell and a space group of Im3. This structure consists of square, planar rings of four pnicogen atoms (i.e., X from the general formula) with rings of four oriented along either the (100), (010), or (001) crystallographic directions. The metal atoms M form a simple cubic sublattice, and the rattler atoms R are positioned in the two remaining holes in the unit cell. The structure of filled skutterudites differs from basic skutterudites in that basic skutterudites do not contain a rattler atom R. It has previously been shown that the κlattice of filled skutterudite antimonides is nearly an order of magnitude lower than that of the basic skutterudites due to the presence of the rattling atoms R.
  • Filled skutterudites are difficult to synthesize in pure form by conventional arc melting processes. Moreover, the observed low κ[0015] lattice of these filled skutterudite antimonides is still significantly higher than the predicted κmin. There are a few possible sources for this problem, one of which is the presence of impurity phases such as RX2 or MX2. Another possible source may be that the filled skutterudites generated thus far are not actually similar to phonon glasses. Thus, the R elements used likely do not have sufficiently large anharmonic deflection to allow the skutterudites to approach the phonon glass limit.
    • SUMMARY OF THE INVENTION
  • The present invention overcomes the problems outlined above and provides new methods for the production of desirable high T[0016] c and Jc (both magnetic and transport) value Hg-containing film superconductors having significantly improved epitaxial characteristics. As is conventional in the art, transport Jc refers to the measure of current density through a film when a current is directly applied to the film whereas magnetic Jc refers to the measure of current density through a film that is induced by the application of a magnetic field to the film. The present invention also provides methods for the production of thermoelectric materials having high ZT's and low -thermal conductivities. As is conventional in the art, ZT=TS2/κρ, where T is the maximum operating temperature of the material, S is the Seebeck coefficient, ρ is the resistivity, and κ is the thermal conductivity of the material.
  • Generally speaking, the processes of forming superconductor films involves initial production of T1-based superconducting films using known T1-vapor annealing techniques, followed by Hg-vapor annealing to replace at least a portion of the T1 by Hg so that the desired Hg-based superconducting films are obtained. T1-based superconducting films have similar crystalline structures to Hg-based superconducting films, but the T1 and especially J[0017] c values at high temperature above 77K of the T1-films are much lower. However, T1 is much less volatile than Hg and has a higher sticking coefficient. These factors make it much easier to grow T1-based superconducting films that have greatly superior epitaxial properties (i.e., the grains are more uniformly aligned and are not randomly positioned on the substrate) compared to prior art films. When such precursor films are placed in an Hg-vapor environment and heated to elevated temperatures, T1 is driven out of the starting films and replaced by Hg simultaneously. Using appropriate time/temperature annealing conditions, it has been found that this exchange can occur without significantly altering the overall crystalline structure, so that high quality epitaxial Hg-based superconducting films can be obtained.
  • Thus, the methods of the invention broadly involve first providing a body made up of a substrate having a T1-based superconducting film supported on a surface thereof, followed by annealing the body in the presence of Hg vapor and under conditions whereby at least a portion of the T1 of the starting superconducting film is replaced by Hg. Generally, this Hg-vapor annealing is carried out at a temperature of from about 600-900° C. for a period of from about 1-20 hours, and more preferably at a temperature of from about 640-800° C. for a period of from about 2-15 hours. [0018]
  • In applications where it is desirable to form micro-bridges, the T1-based superconducting film is patterned and etched using conventional photolithography and etching techniques (i.e., a photoresist composition is applied to the film, exposed to activating radiation, developed, and etched). The remaining T1 film and newly formed micro-bridges are then annealed in the presence of Hg vapor as described above. The width of the micro-bridges is generally from about 2-10 m. [0019]
  • The most desirable T1-based starting superconducting films for making Hg-1212 superconducting films are selected from the group consisting of T1-1212 and T1-2212 films (i.e., T1Ba[0020] 2CaCu2O7 and T12Ba2CaCu2O8), preferably yielding HgBa2CaCu2Ox films wherein x ranges from about 5.8-6.2. The most desirable T1-based starting superconducting films for making Hg-2223 superconducting films are selected from the group consisting of T1-1223 and T1-2223 (i.e., T1Ba2Ca2Cu3O9 and T12Ba2Ca2Cu3O105), preferably yielding HgBa2Ca2Cu30x films wherein x ranges from about 7.8-8.2. These are generally formed on a substrate, usually a single crystal substrate such as LaAlO3, by known techniques to form a highly epitaxial film.
  • The Hg-vapor annealing step can be carried out in a number of different ways. FIG. 1 sets forth a number of different orientations of the starting T1-film bodies (shown as rectangles) with respect to a superconducting Hg-containing pellet and optionally in the presence of a Ba—Ca—Cu—O oxide pellet. It will be understood that these various annealing configurations are in practice preferably placed within a quartz tube (not shown in FIG. 1) whereupon a vacuum (on the order of from about 10[0021] −4 to 1 Torr) is drawn and the tube is sealed. This sealed tube is then placed within the annealing furnace.
  • The final Hg-containing films are preferably either Hg-1212 or Hg-1223 films and usually have a thickness of from about 0.005-500 μm and more preferably from about 0.1-1 μm. In addition, the final Hg-containing films and micro-bridges formed of these films have very high transport and magnetic Jc values of at least about 10[0022] 6 A/cm2, preferably at least about 2×106 A/cm2, and more preferably at least about 2.3×106 A/cm2 at 100K and zero magnetic field and Tc values of from about 112-125K for Hg-1212 films (as used herein, Tc values refer to Tc (R=0), rather than onset Tc onset values). These Jc values are quite significant because the prior art Hg-containing films, and particularly Hg-1212 films, have only been able to achieve Jc values of 106 A/cm2 at 77K and zero magnetic field. Furthermore, these prior art Jc values are magnetic Jc values and not transport Jc values. Because Jc depends on both the superconductivity of the molecule applied to the substrate as well as the manner in which the molecule grains are positioned on the substrate (i.e., the epitaxy), the current densities of films at higher temperatures are unpredictable based upon the current densities of the films at lower temperatures. The highly epitaxial character of the Hg-containing films of the invention is confirmed by the x-ray pole figures and Xmin values thereof which are up to about 50%, and more preferably from about 10-40%. Finally, Hg-1212 films according to the invention have a low microwave surface resistance of less than about 0.4 mΩ and preferably less than about 0.3 mΩ at 120K, values that have never been obtained above 100K in prior art superconductors.
  • The processes of forming thermoelectric materials according to the invention comprises providing, in a reaction vessel, a three-dimensional, crystalline precursor comprising a plurality of atoms and at least one molecule weakly bonded thereto. As used herein, molecule is intended to include elements as well as ions derived from those elements. For example, “lanthanum molecule” is intended to include elemental lanthanum as well as lanthanum ions. [0023]
  • The precursor is then perturbed, causing the bond(s) between the molecule and the atoms to break, thus releasing the molecule from the precursor. The perturbing step can be accomplished by any method which subjects the crystalline precursor to energy of perturbation. Suitable methods include heat, light, ion beams, etc. When heat is utilized, the temperature to which the precursor is heated should be at least about 500° C., and preferably at least about 1000° C., depending upon the particular molecule which is weakly bonded to the precursor. [0024]
  • Either simultaneous to or shortly after the perturbing step, vapor under a controlled pressure and comprising a second molecule is introduced into the reaction vessel so that the second molecule replaces the released first molecule within the precursor. Preferably, the remaining crystalline structure of the precursor (i.e., structure other than the first molecule) remains essentially unaltered during this process. [0025]
  • Generally, any crystalline structure can be utilized as the crystalline precursor in the inventive processes, with body-centered crystals, orthorhombic crystals (such as perovskites), and cubic crystals being particularly preferred. One suitable type of body-centered crystal is the skutterudite having the general formula RM[0026] 4X12, where M is a metal atom and R is a “rattler.” Preferred metal atoms M are Fe, Ru, and Os, while preferred rattlers R (for use as the first molecule) are selected from the group consisting of La, Ce, Pr, Nd, and Eu. “X” in the general formula RM4X12 is preferably a pnicogen atom (e.g., P, As, Sb).
  • Any volatile molecule that is desired in the precursor at the same location as the first molecule can be utilized as the second molecule. Again, the same definition of molecule discussed above is intended to apply with respect to the second molecule. Thus, if a vapor of Hg is utilized, that vapor could comprise elemental Hg or Hg ions. Examples of suitable candidates for second molecules include those selected from the group consisting of Pb, Hg, Sn, In, T1, and Ga. Because the second molecule is more volatile than the first molecule, it will have increased “rattling” abilities compared to the first molecule (i.e., increased local anharmonic vibrations around the rattler site). Thus, due to the presence of the volatile second molecule, the resulting thermoelectric materials have a phonon thermal conductivity (κ[0027] lattice) at room temperature of less than about 0.012 W/cm-K, preferably less than about 0.01 W/cm-K, and more preferably less than about 0.007 W/cm-K. This low -κlattice contributes to thermoelectric materials having a ZT of at least about 2, preferably at least about 3, and more preferably at least about 3.5.
    •  BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is a schematic representation of a number of exemplary annealing configurations which can be used in the preparation of the thin film superconductors of the invention; [0028]
  • FIG. 2 is a scanning electron micrograph (SEM) of an exemplary Hg-1212 film (Run No. 3 of the Example) exhibiting condensed plate-like grains; [0029]
  • FIG. 3 is a series of XRD θ-2θ scans of a T1-2212 original film and two Hg-1212 films (TLHG-C and SY1112L refer to Runs Nos. 3 and 14, respectively) after substitution conversion from T1-2212 films; [0030]
  • FIG. 4 is a series of XRD θ-2θ scans of a T1-1212 original film and two Hg-1212 films (X971202 and X971123 refer to Runs Nos. 20 and 24, respectively) after substitution conversion from T1-1212 films; [0031]
  • FIG. 5 is a series of critical transition curves of an original T1-2212 film and of some Hg-1212 films after substitution conversion from T1-2212 films (TLHG.D, SY1112, TLHG.F, TLHG.G, TLHG.H, TLHG.L2, TLHG.C, TLHG.I and TLHG.J refer to Runs Nos. 4, 14, 5, 10, 11, 9, 3, 6 and 7, respectively); [0032]
  • FIG. 6 is a series of critical transition curves of an original T1-1212 film and some Hg-1212 films after substitution conversion from T1-1212 films (TH1212B, Y980121, X971204, TH1212A, X971126, X971123 and X971202 refer to Runs Nos. 23, 22, 25, 21, 26, 24 and 20, respectively); [0033]
  • FIG. 7 is an XRD pole figure of a Hg-1212 film (Run No. 3); [0034]
  • FIG. 8 is a series of critical current densities of an original T1-2212 film and of three Hg-1212 films after substitution conversion from T1-2212 films (SY1112L, TLHG.C, TLHG.D refer to Runs Nos. 14, 3 and 4, respectively); [0035]
  • FIG. 9 is a series of critical current densities of an original T1-1212 film and of five Hg-1212 films after substitution conversion from T1-1212 films (TH1212A, TH1212B, X971123, X971126, X971202 and X971204 refer to Runs Nos. 21, 23, 24, 26, 20 and 25, respectively); [0036]
  • FIG. 10 is a graphical comparison of the critical current density (J[0037] c) of representative Hg-1212 film (Run No. 3) and T1-2212 film in different magnetic fields at 60 K, 77 K and 100 K;
  • FIG. 11 is a graph illustrating the critical current density of a representative Hg-1212 film (Run No. 3) at varying magnetic fields and at different temperatures; [0038]
  • FIG. 12 is a graph similar to that of FIG. 11 and illustrates a series of critical current density readings for the same Hg-1212 film (Run No. 3) in lower magnetic fields (<0.1 T) and at higher temperatures (≧70 K); [0039]
  • FIG. 13 is a graph illustrating RBS/channeling results with a representative Hg-1212 film (Run No. 4); the calculated X[0040] min˜40% indicates the alignment of more than 60% of the grains of the film in the plane of the LaAlO3(001) substrate;
  • FIG. 14 is a graph illustrating the transport critical current density (J[0041] c) at varying temperatures of an Hg-1212 film prepared according to the processes of the invention;
  • FIG. 15 is a graph illustrating the microwave surface resistance of T1-2212 and Hg-1212 films processed according to the processes of the invention; [0042]
  • FIG. 16 is an SEM photograph showing Hg-vapor annealed T1-2212 micro-bridges having widths of 20 μm, 10 μm, and 2 μm at magnifications of 2000×, 1500×, and 3000×; [0043]
  • FIG. 17 is an SEM photograph (1100×) showing Hg-1212 micro-bridges having widths of 20 μm and 10 μm; [0044]
  • FIG. 18 is a graph illustrating the resistance vs. temperature behaviors of H-1212 micro-bridges processed according to the processes of the invention and annealed at 780° C.; [0045]
  • FIG. 19 is a graph illustrating the resistance vs. temperature behaviors of H-1212 micro-bridges processed according to the processes of the invention and annealed at 700° C.; and [0046]
  • FIG. 20 is a graph illustrating the transport critical density (J[0047] c) at varying temperatures of Hg-1212 micro-bridges having varying widths and processed according to the processes of the invention and annealed at 780° C. (“HT”) and 700° C. (“LT”).
    • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
  • The following example sets forth preferred techniques for the production of metal-substituted superconducting epitaxial thin films, as well as characterizing results for the films. The examples also describe preferred methods of fabricating the inventive thermoelectric materials. It is to be understood that these examples are provided by way of illustration only, and nothing therein should be taken as a limitation upon the overall scope of the invention. [0048]
    • Fabrication of Superconducting Films
  • Examples 1-4 are directed towards methods of forming superconducting films according to the processes of the invention. [0049]
    • EXAMPLE 1
  • In this example, a series of Hg-1212 epitaxial films were produced using the Hg substitution technique. In the first step, a series of approximately 3×3×0.5 mm single crystal lanthium aluminate (LaAlO[0050] 3) blocks were provided. A surface of each of these blocks was coated with either T1-2212 (T12Ba2CaCu2O8) or T1-1212 (T1Ba2CaCu2O8) using the DC magnetron sputtering technique as described by Yan et al., Appl. Phys. Lett., 63:1845 (1993); Yan et al, Supercond. Sci. Technol., 7:681 (1994) and Siegal et al, J. Mater. Res., 12:2825 (1997). Thereafter, the coated blocks were annealed at a temperature of about 740-780° C. for a period of about 6 hours in an enclosed crucible formed of either solid T12Ba2CaCu2O8 (for the T1-2212 coated blocks) or T1Ba2CaCu2O65 (for the T1-1212 coated blocks), with pure argon gas. This created an epitaxial film of superconducting T12Ba2CaCu2O8 or T1Ba2CaCu2O65 on the blocks. These epitaxial films had a thickness of about 0.3 μm. The epitaxial nature of the films was confirmed by XRD pole figure and RBS/channeling.
  • In the next step, each of the blocks was subjected to Hg substitution to create epitaxial Hg-1212 films thereon. Generally speaking, this was accomplished by placing the blocks adjacent an Hg-containing body (Hg[0051] 1-yBa2Ca2Cu3Ox, wherein y ranged from 0-0.5), and sometimes an additional body of non Hg-containing oxide (a mixture of BaO, CaO and CuO in a nominal 223 ratio) in a quartz tube (7 mm I.D., 10 mm O.D., 2.5 cm in length). One end of the quartz tube was then closed and a vacuum (˜10−2 Torr) was drawn in the tube, whereupon the remaining end of the quartz tube was fused. The closed quartz tube was then placed within an elongated stainless steel pipe (about ½ inch I.D.) and this was placed within a conventional tube furnace. At this point, the contents of the quartz tube were heated at an ascending rate of 10-50° C./min. to an annealing temperature, the annealing temperature was held for a period of hours (annealing period), and thereafter the quartz tube was furnace cooled until ambient temperature was reached.
  • The Hg-containing bodies were in the form of cylindrical pellets (6 mm diameter×4-10 mm length) and in some cases these were slotted to receive the previously coated blocks. In other instances, the blocks were placed adjacent one end of the Hg-containing superconducting body, or sandwiched between two such bodies. Similarly, where the precursor bodies were used, these were in the form of 6 mm diameter pellets of variable length. FIG. 1 illustrates various exemplary block/pellet configurations, some of which were used in these experiments. The Hg-containing and non-Hg-containing bodies can be reacted or unreacted. [0052]
  • The individual blocks having the substitution-formed Hg-1212 epitaxial superconducting thin films thereon were recovered and further annealed in a tube furnace at a temperature of 300-350° C. for a period of from about 1-10 hours in a flowing oxygen enviromnent to maximize the T[0053] c of the final films. During this final annealing step, the furnace was heated at a rate of approximately 15° C./min. up to 300° C., and after the annealing was completed, the blocks were cooled by turning off the furnace power.
  • The resultant Hg-substituted thin film superconductors were evaluated for T[0054] c, Jc at 5, 77 and 100K, surface morphology and structure, Xmin, and in some instances phase purity.
  • Table 1 below sets forth the annealing conditions employed in the formation of the Hg-1212 superconducting films using the T1-2212-coated blocks. [0055]
    TABLE 1
    Pellet Composition
    Annealing Annealing
    Temperature Period Annealing Configuration Wt. Ratio of Hg-Pellet to
    Run # (° C.) (Hrs.) (see Fig. 1) Hg-Pellet Non Hg-Pellet Non-Hg Pellet
    1 800 3 H HgBa2Ca2Cu3Ox Ba2Ca2Cu3Ox 3:1
    2 790 3 H HgBa2Ca2Cu3Ox Ba2Ca2Cu3Ox 3:1
    3 780 3 H HgBa2Ca2Cu3Ox Ba2Ca2Cu3Ox 3:1
    4 770 3 H HgBa2Ca2Cu3Ox Ba2Ca2Cu3Ox 3:1
    5 770 6 H HgBa2Ca2Cu3Ox Ba2Ca2Cu3Ox 3:1
    6 760 3 H HgBa2Ca2Cu3Ox Ba2Ca2Cu3Ox 3:1
    7 750 3 H HgBa2Ca2Cu3Ox Ba2Ca2Cu3Ox 3:1
    8 780 3 L Hg2Ba2Ca2Cu3Ox Ba2Ca2Cu3Ox 3:1
    9 780 3 H HgBa2Ca2Cu3Ox Ba2Ca2Cu3Ox 3:1
    10 770 3 H Hg2Ba2Ca2Cu3Ox Ba2Ca2Cu3Ox 3:1
    11 770 3 H HgBa2Ca2Cu3Ox Ba2Ca2Cu3Ox 3:1
    12 740 3 F Hg0.5Ba2Ca2Cu3Ox — —
    13 740 10 F Hg0.5Ba2Ca2Cu3Ox — —
    14 700 12 B Hg0.5Ba2Ca2Cu3Ox — —
    15 690 12 B Hg0.5Ba2Ca2Cu3Ox — —
    16 640 12 B Hg0.5Ba2Ca2Cu3Ox — —
    17 610 12 A Hg0.5Ba2Ca2Cu3Ox — —
    18 720 12 A Hg0.5Ba2Ca2Cu3Ox — —
    19 780 3 H HgBa2CaCu2Ox Ba2CaCu2Ox 3:1
  • Table 2 sets forth the characterizing data developed from testing the films of Table 1. [0056]
    TABLE 2
    Run Tc Jc (× 106 A/cm2) Phase Purity
    # (K) 5K 77K 100K (%) Surface Morphology Structure
    1 115 1.63 — — 93.6 Plate-like grains and impurity C-axis
    particles oriented
    2 115 5.79 0.38 0.13 94.2 Plate-like grains and impurity C-axis
    particles oriented
    3 120 13.1 2.23 0.91 89.6 Bright, dense plate-like grains C-axis
    oriented
    4 120 14.0 2.78 0.95 79.9 Bright, plate-like grains and small C-axis
    holes oriented
    5 120 10.9 1.12 0.37 85.4 Bright, dense plate-like grains C-axis
    and small holes oriented
    6 120 14.9 1.57 0.53 66.5 Plate-like grains and small holes C-axis
    oriented
    7 117 10.5 0.94 0.26 76.5 Plate-like grains and small holes C-axis
    oriented
    8 122 6.1 0.70 0.20 88.8 Plate-like grains and tiny parti- C-axis
    cles oriented
    9 120 17.2 1.96 0.83 87.9 Dense plate-like grains C-axis
    oriented
    10 120 16.1 1.98 0.82 85.0 Plate-like grains and small holes C-axis
    oriented
    11 120 18.1 1.92 0.64 63.0 Plate-like grains and small holes C-axis
    oriented
    12 — — — — 70.0 Dense small grains C-axis
    oriented
    13 — — — — 50.0 Plate-like grains and holes C-axis
    oriented
    14 124 22.6 3.09 1.18 96.0 Bright dense uniform surface C-axis
    oriented
    15 118 16.5 — — 82.0 Bright dense uniform surface C-axis
    oriented
    16 — — — — 65.0 Bright dense uniform surface C-axis
    oriented
    17 — — — — 10.0 Bright dense uniform surface C-axis
    oriented
    18 120 17.7 1.81 0.71 85.0 Plate-like grains and holes C-axis
    oriented
    19 122 — — — —
  • Table 3 below gives the annealing conditions used in the formation of the Hg-1212 superconducting films using the T1-1212-coated blocks. [0057]
    TABLE 3
    Annealing Annealing Film and
    Run Temperature Period Pellets Pellet Composition Wt. Ratio of Hg-Pellet
    # (C °) (Hrs.) Position Hg-Pellet Non Hg-Pellet to Non-Hg Pellet
    20 810 3 A HgBa2Ca2Cu3Ox — —
    21 780 3 H HgBa2Ca2Cu3Ox Ba2Ca2Cu3Ox 3:1
    22 780 3 H HgBa2Ca2Cu3Ox Ba2Ca2Cu3Ox 3:1
    23 750 3 H HgBa2Ca2Cu3Ox Ba2Ca2Cu3Ox 3:1
    24 750 20 A HgBa2Ca2Cu3Ox Ba2Ca2Cu3Ox 3:1
    25 750 20 A Hg0.75Ba2Ca2Cu3Ox —
    26 750 20 A Hg0.5Ba2Ca2Cu3Ox —
  • Table 4 gives the characterizing data developed from testing the films of Table 3. [0058]
    TABLE 4
    Jc (× 106 A/cm2) Phase Purity Surface
    Run # Tc(K) 5K 77K 100K (%) Morphology Structure
    20 112 22.7 9.4 × 10−3 — — smooth C-axis oriented
    21 115 13.6 0.88 0.04 — smooth C-axis oriented
    22 122 21.2 1.1 0.11 — smooth C-axis oriented
    23 115 16.1 0.98 0.01 — smooth C-axis oriented
    24 117 19.4 1.0 0.2 — smooth C-axis oriented
    25 114 23.5 1.2 0.4 — smooth C-axis oriented
    26 112 24.2 0.8 0.2 — smooth C-axis oriented
  • FIGS. [0059] 2-13 further exemplify the characteristics of the Hg-containing superconducting thin films of this example. Thus, in FIGS. 5 and 6, critical temperature transition curves are provided which confirm that the Tc values of the T1-containing films are substantially lower than those of the substituted Hg-containing films. Likewise, FIGS. 8-10 set forth critical current density data and establishes that at high temperature (>90K), the critical current densities of the Hg-1212 films are much larger than those of the T1-1212 and T1-2212 films.
    • EXAMPLE 2
  • In this example, an Hg-1212 epitaxial film was produced following the procedures set forth in Example 1. The resultant Hg-substituted thin film superconductor was evaluated for transport J[0060] c at 100K and varying magnetic fields. The results of this evaluation are depicted in FIG. 14 where it can be seen that the transport Jc at zero magnetic field was 106 A/cm2.
    • EXAMPLE 3
  • In this example, an Hg-1212 epitaxial film was prepared following the procedures set forth in Example 1. The intermediate T1-2212 film and the resultant Hg-substituted film were evaluated for their microwave surface resistance at 10 GHz and varying temperatures. As illustrated in FIG. 15, at 115 K and 10 GHz, a resistance of 0.3 milliohms was observed for the Hg-1212 films. This resistance has never been achieved at 115K by prior art films. [0061]
    • EXAMPLE 4
  • In this example, T1-2212 films were prepared as described in Example 1. The films were then etched using conventional photolithography processes to form micro-bridges of various widths in the film. The T1 forming the micro-bridges was then replaced by Hg also as described in Example 1, with three micro-bridges each being annealed at 780° C. for 3 hours (SEM of bridges shown in FIG. 16) and two micro-bridges each being annealed at 700° C. for 12 hours 10 (SEM of bridges shown in FIG. 17). FIGS. 18 and 19 depict the resistivity versus temperature of the bridges while FIG. 20 illustrates the transport J[0062] c. The Tc values of these micro bridges are in the range of 110-120K and the transport Jc values are in the range of 0.5 to 2.3×106 A/cm2 at 100K and 0 magnetic field. A value of 2.3×106 A/cm2 at 100K has not been achieved by prior art superconductors. These results indicate that Hg-based superconducting microelectronic devices can be converted directly from T1-based superconducting devices.
    • Fabrication of Thermoelectric Materials
  • A similar process as that described above with respect to films can be utilized to synthesize highly volatile compounds which would otherwise be difficult, if not impossible, to synthesize. First, a precursor matrix is selected. The matrix should have a similar structure and composition to that of the final, target material. The matrix should also have at least one weakly bonded molecule (e.g., “molecule A”) which will be replaced by the desired molecule (e.g., “molecule B”) to form the target material. Molecule A is perturbed (i.e., energy is applied to the precursor matrix), causing molecule A to vibrate around the equilibrium site where the Gibbs free 25 energy is minimized. It will be appreciated that the spacial deflection of molecule A is proportional to the energy of perturbation. In the inventive processes, the perturbation energy is maintained close to, but below, the threshold perturbation energy (U[0063] th). Uth is the point at which the deflection of molecule A would be comparable to the lattice constant, thus causing the precursor matrix to collapse as a result of the rapid escape of many molecules A from the matrix. By maintaining the perturbation energy below Uth, the overall structure of the precursor is maintained while allowing molecule A to slowly escape. A vapor of molecule B is simultaneously introduced, resulting in a molecule B replacing essentially each molecule A as it escapes from the structure.
  • One type of material particularly useful in this process is the skutterudite. Skutterudites filled with volatile rattlers can be fabricated from basic skutterudites (i.e., MX[0064] 3, where M is a metal atom and X is preferably a pnicogen atom) or from skutterudites filled with less volatile (relative to the rattlers) molecules.
  • This process offers numerous advantages over the prior art. First, it is a kinetic process that can be carried out over a wide processing window in contrast to the narrow processing window required by the phase equilibrium of conventional thermal reaction processes. Also, the exchange occurs at an atomic scale. Therefore, the generated compound inherits the qualities (e.g., phase purity, crystalline structure, surface morphology) of the precursor matrix. This makes synthesis of the compounds much simpler and improves the quality of the final compounds as the precursor matrices are generally readily obtainable in high quality forms. [0065]
  • The remaining Examples are directed towards the preparation of improved thermoelectric materials according to the invention. [0066]
    • EXAMPLE 5
  • Basic, non-filled skutterudites are prepared according to the known prior art methods. The skutterudites are then heated in an evacuated vessel to temperatures of from about 500-1000° C. Hg vapor is simultaneously introduced into the vessel at a vapor pressure of from about 1-10 atm, causing Hg molecules to fill the skutterudites after a time period of about 30-200 minutes. [0067]
    • EXAMPLE 6
  • Skutterudites filled with Pb molecules are prepared according to known prior art methods. The Pb-filled skutterudites are then heated in an evacuated vessel to a temperature of at least about 500° C. While the vessel is maintained at this temperature, Hg vapor is introduced into the vessel at a vapor pressure of from about 1-10 atm so that Hg molecules replace the Pb molecules as they are released from the skutterudites, forming skutterudites filled with Hg molecules. [0068]

Claims (18)

We claim:
1. An Hg-1212 epitaxial film superconductor having a Jc of at least about 106 A/cm2 at 100K and zero magnetic field.
2. The film of claim 1, said film having a thickness of from about 0.005-500 μm.
3. The film of claim 2, said thickness being from about 0.1-1 μm.
4. The film of claim 1, said film being HgBa2CaCu20x where x ranges from about 5.8-6.2.
5. An Hg-containing epitaxial film superconductor having a Xmin of up to about 50%.
6. The film of claim 5, said film having a thickness of from about 0.005-500 μm.
7. The film of claim 6, said thickness being from about 0. 1-1 μm.
8. The film of claim 5, said film being HgBa2CaCu30x where x ranges from about 7.8-8.2.
9. The film of claim 5, said film having a Jc of at least about 106 A/cm2 at 100K and zero magnetic field.
10. An Hg-containing epitaxial film superconductor having a transport Jc of at least about 106 A/cm2 at 100K and zero magnetic field.
11. The film of claim 10, said film having a thickness of from about 0.005-500 μm.
12. The film of claim 11, said thickness being from about 0.1-1 μm.
13. The film of claim 10, said film having a transport Jc of at least about 2×106 A/cm2 at 100K and zero magnetic field.
14. The film of claim 13, said film having a transport Jc of at least about 2.3×106 A/cm2 at 100K and zero magnetic field.
15. The film of claim 10, said film being in the form of micro-bridges having a width of from about 2-10 μm.
16. The film of claim 15, said film micro-bridges having a transport Jc of at least about 2.3×106 A/cm2 at 100K and zero magnetic field.
17. An Hg-containing epitaxial film superconductor having a microwave surface resistance of less than about 0.4 mΩ at 120K.
18. The film of claim 17, said film being an Hg-1212 film.
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